Continuous production of hexachlorcyclopentadiene



United States Patent This invention relates to an improved process for the production of hexachlorcyclopentadiene from aliphatic hydrocarbons by reaction with chlorine. In particular it relates to a process for the production of hexachlorcyclopentadiene in the gas phase with the use of new catalysts which are gaseous or which exist in the gas phase under the reaction conditions.

It is already known that hexachlorcyclopentadiene is obtained when aliphatic hydrocarbons with carbon atoms or five-membered cycloaliphatic hydrocarbons are heated with at least the calculated amount of chlorine.

without or in the presence of solid catalysts to temperatures of about 350 to 550 C. Polychlor compounds of the said hydrocarbons have also already been converted into hexachlorcyclopentadiene by heating, preferably in the presence of chlorine. These methods have the disadvantage that without a catalyst only unsatisfactory yields of the perchlorinated cyclopentadiene are obtained besides considerable amounts of lay-products. When working with the use of solid catalyst, for example barium sulfate (cf. German patent specification No. 959,093) it is true that better yields, and in some cases quite good 35 yields, of hexachlorcyclopentadiene are obtained, but the solid catalysts have the disadvantage that by reason of the deposits precipitated thereon they stick and become catalytically inactive so that'replacement of catalyst be comes necessary.

In order to obviate this disadvantage attempts have therefore already been made to carry out the reaction in several stages by reacting pentane with chloride in the presence of light to form more or less highly chlorinated pentanes and leading the chlorine compounds, possibly 1 with the addition of further chlorine, at elevated temperature over the solid catalysts. A more recent process consists in leading polychlorpentane with chlorine through a reaction zone at least partly charged with catalyst, of which the temperature continually rises from about 280 to 350 C. to about 375 to 550 C. from the inlet side of the reaction materials to the outlet side thereof, the. undesirable reaction products being returned to the reaction zone. Apart from the fact that in the reaction which proceeds with evolution of heat, the maintenance of the temperature gradient ofiers difliculty and requires special precautions, the disadvantages which attend working with solid catalysts by reason of the deposits precipi-' tated thereon, namely the subsidence of the activity and ucts canonly beseparated with difiiculty from the h'exa- ICEv 2 n chlorcyclopentadiene. This process therefor e has little appeal for carrying out in practiceand on a technical scale.

cyclopentadiene according to which,hexachlorcyclopentadiene is obtained in 'a simple'manner easily carriedv 'out industrially and the said disadvantages of the. prior proposals are'avoided.

It is an object of this invention to provide a continuous process'for the production of hexachlorcyclopentadiene which is suitable for carrying out on a large technical,

scale. A further object is to provide new'catalysts for theproduction of hexachlorcyclopentadiene from aliphatic open-chain and cycloaliphatic hydrocarbons .withfive j carbon atoms and chlorine which makes it possible to carry out the reaction in'the simplest possible apparatus with high throughputs and good space-time yields, as well as total yields, of hexachlorcyclopentadiene; "Yet a.

further object is to provide'new catalyst which show a strongly selective and high activity for the formation of hexachlorcyclopentadiene in the said reaction, cannot give rise to operational and reaction disturbances in the reaction zone and can be readily separated from there chain, cyclopentane, cyclopentene, cyclopentadiene and dicyclopentadiene is led in vapor phase: with gaseous chlorine continuously through a reaction zone heated to at least 200' C., preferably about 300 to 500 C., at the same time at least one inorganic or organic nitrogenous compound gaseous under the reaction conditions from the group consisting of oxides of nitrogen, nitrogen oxychlorides, amines of the aliphatic, alicyclic, aromatic and heterocyclic series, benzonitrile, monocarboxylic acid nitriles, unsubstituted monocarboxylic acid amides of alkane and alkene carboxylicfacids with up to 6 carbon atoms and arnides of the said kind substituted once or twice by N-alkyl with 1 to 4 carbon atoms, and cyclic V N-unsubstituted and N-methyl-to-butyl substituted carboxylic acid amides in which the amido group forms a ring with 3 to 5 CH groups, is led in, so that the reaction components andthe vapcrous catalyst flow through the zone together, the vapors leaving the zone are condensed and the hexachlorcyclopentadiene is separated from the condensate.

Of the inorganic nitrogen compounds described as catalysts there may be mentioned especially dini-trogen oxide (N 0), also known under the names laughing gas and nitrous oxide, nitrogen monoxide (NO) often known briefly as'nitrogen oxide or nitric oxide, and nitrogen' dioxide (N0 As nitrogen oxychlorides there may be mentioned nitrosyl chloride (N-0C1) and nitryl chloride (:NO Cl). there may be mentioned among the amines of the aliphatic, alicyclic and aromatic series above all the primary, secondary and tertiary .alkylamines and cycloalkylamines as well as aniline, N-alkylanilines and N.N-dialkylanilines; and mixed alkyl-cycloalkylamines. It is preferable to choose forthe alkylamines alkyl radicals with 1 to 8 carbon atoms, those. with 1 to 4 carbon atoms being preferred. As 'cycloalkylamines there come into. question those with up to 6 carbon atoms, preferably. those with 5 or 6 carbon atoms in the ring, and if desired the cycloalkyl groups may have on the ring one ortwo methyl to butyl groups. Amines which we prefer are Patented July 19, 196thv The object of the present invention is to provide a: new improved process for the production of hexachlor 7 Of 'the reaction-promoting organic substances for example methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, normaibutylamine, dibutylamine, ethylbutylamine, octylamine and-Z-ethylhexylamine, and also cyclohexyl amine cyclopentylamine, N-.N'-dimethyl-cyclohexylamine,-

N N-diethyb, dipropyland -dibutyl-cyclohexylamine, N-

methyl-N-butylcyclohexylamine and N.N-dimethyl-2- or- -4-rne thyl--- cyclohexylamine, aniline,- N methylaniline, N.N-dirnethylaniline and N-butylaniline- Of-the heterocyclic amines there maybe mentioned asgroups, on, the. ring carbon atoms or on the-nitrogenatom so -far .as it contains a. replaceable hydrogenatom. As-heterocyclic amines there therefore comemto question both secondary and-tertiary amines. There may be mentioned for example pyridine, picoline, pyrrolidine, piperidine, hexamethylene imine and N-methylpyrrolidine. Heterocyclic amines which contain anoxygen atom combined in.thel-lleterocyclic ring, as well as the N-hetero atom, for example morpholine, may also be used.

The .monocarboxylic acid nitriles of alkaneand alkene carboxylic acids with.up. to -8 carbon atoms may be unbranched,; i.e; straightachained, or branched. Mononitrilesofsaturated and unsaturated aliphatic carboxylic acids '.WhlCh; have.1 to..4:,carbon .atoms in the alkyl or alkenyl radicals are especially suitable. There may be mentionedfor..exampleacetonitrile, propionitrile, butyrolnitrile, valeronitrile, caprylic. nitrile and oenanthic nitrile aswell as of the unsaturated nitrilesabove all, acrylonitrile andmethacrylonitrilea Mononitriles of aromatic caLbOXy1iC; -30idS, for, example of benzoic acid, may also be used.

As acid amides there may serve accordingto this inventionopen-chainand cyclic combined monoamides in which thegroup which the amide groupis combined is arranged in a .5

straight chain or branched. Open-ch ain acid amides are for example tormamide, acetamide, -N-methylformamide, N-ethylacetamide, N.N dimethylformamide,; N.N-dibutyltormamide, N-butylacetamide, propionamide, butyramide, iso;butyramide, caproic acid .amide and oenanthic acid amide as well as their N-monoand' N.N- dis ubstituted methyl, ethyl, propyl and butyl derivatives. Of the cyclic amides with ring-combined amide groups those are the most important and best suitable in which the ring is formed from a CONH- group or CONR-group (R being methyl to butyl) and 3 to 5 CH groups, i.e. methylene groups.- As, representative of the preferred cyclic amides there may be mentioned pyrrolidone, N- methylpyrrolidone, N-butylpyrrolidone, N-propylpyrrolidone and N-ethylpyrrolidone.

The amounts in which the catalysts are co-employed in the reaction can vary within .wide limits. Although even by the addition of less than 0.1% by weight with ref- 1 erence to the amount of initial hydrocarbon used, a clear reaction-promoting action occurs, it is preferable to add the catalysts in amounts of 0.2% or more, for example up to about 10% by weight. It is especially advantageousto work with about 1 to 5% by weight. When the co-employed catalysts are not already gaseous at room temperature, they may be brought in the stated 7 amounts in liquid or solid form into thereaetion .2911;

where they then immediately become vaporous. They may however first be vaporized and then introduced into the reaction zone as such or together with one of the reaction components or with a mixture of the initial hydrocarbon and chlorine.

The reaction takes place in homogeneous vapor phase at temperatures of at least 200 C. In general operation is preferably in a temperature range of about 300 C. to about 500 C., advantageously between about 320 and 420 C. The most favorable reaction temperatures are to a slight extent different for the different initial hydrocarbons and the co-employed catalysts. The most advantageous temperatures may be readily ascertained by preliminary experiment. The reaction may be carried out by leading the vapor of .pentane or of mixtures of various initial hydrocarbons through a reaction zone heated to the reaction temperature and at the same time introducing chlorine and the catalyst in vapor form into the zone. It is preferable to mix the vaporous catalyst with the initial hydrocarbon prior to entry into the reaction zone and then to leadthe mixture, if desired preheated up to near to the reaction temperature, into the reaction zone together with chlorine. may take'place for example in heat exchange with the reaction product leaving the zone. The amount of chlorine is chosen so that the mol ratio of hydrocarbon zchlorine is about 1:8 to 1:15, advantageously 1:10 to 1:11; larger amounts of chlorine may however be used. Inert vaporous or gaseous diluents, as for example nitrogen, rare .gases or hydrogen chloride, may be co-employed in the reaction in amounts of 5 to 50 mols per mol of chlorine.

As the reaction zone there may serve for example a vertical tube of steel, quartz or ceramic material, for example of porcelain or difiicultly fusible glass. The tube, which is preferably heated externally, may also be provided in the interior with guide plates or deflecting plates or may be filled with filler bodies. It is advantageous to introduce the incoming materials into the top of the tube and to withdraw the reaction mixture from the bottom of the tube. When using the catalysts according to this invention,.there is no precipitation or settlement of undesirable residues in the reaction zone, even upon prolonged continuous operation, so that the reaction zone is completely clean for example even after 6 months.

Theworking upfof the.reaction mixture takes place by cooling the vaporous reaction mixture, for example to room temperature. After separation of the substances which have'remained gaseous, the condensed portion can readily befurther separated into its components by distillation. If desired the substances which have remained gaseous may be led at least in part back into the reaction zone.

The hexachlorcyclopentadiene obtained is a valuable intermediate product for the production of polyesters, softeners and pesticides, for example by reacting the hexachlorcyclopentadiene in a Diels-Alder reaction with dienophilic compoundsin a manner known per se.

The following examples will further illustrate this invention but the. invention is not restricted to these examp Example 1 A vertically arranged tube of ceramic material having a diameter of 22 mm. and a length of 2,000 mm. is heated 1 of the sreactionr. are. condensed. About 123 to 128 gramstper, hour of a liquid reaction product are obtained which consists to the extent-of 88 to 91% .by weight of ex achlorcvclopentadiene,, 3' to 16%, of chlorinated ali-:. phatiehydrocarbons, mainly; polychlorpentanes, and. 8 :to

The preheating I of nitrogen monoxide per hour.

reaction zone heated to 300 C. in an amount of 66 gramsper hour and at its entry into the zone, there are simultaneously incorporated therewith through separate supply pipes 250 grams of gaseouschlorine and 3 grams After cooling the vapors leaving the reaction zone to about 25 C.', there areobtained per hour on an average about 241 to 246 grams of -a liquid reaction mixture. The'liquid mixture consists to the extent of about 78% of hexachlorcyclopentadiene, while the remainder consists of about 17% of cyclocontent of the liquefied reaction A product: a r

. ;'j f 1 Y amount 1 reaction liquefied I .E xam hydrocarbon+percent by added nitrogen chlorine temperreaction hexachlorchlorinated compounds ple --weight oicatalyst in g./h. inl./h. l./h. ature products cyclopenaliphatic of higher 1 I C. g./h. tadienein hydrocarboiling percent by bons perpointin weight cent by percent by. I weight weight !2 .n?pe 1 tane+2% n-buty1- 36 140 340 124-129 89-93 5-3 6-4 ame.- x

n-pentane+2 pyridine j86 180 355 119-125 86-90 8-6 6-3 n'-pentane+0.8%pyrrolid.ine .36 80 140 380 124-127 88-90 8-5 4-2 n-pentane+2%=propionitrlle;- 36 -80 160 360 119-123 89-92 5-4 '5-3 n-pentane-t-IZ, acrylonitrile. 36 40 160 355 121-126 90-92 6-5 4-2 n-pentane+3% benzonitrile. 36 40 160 355 113-117 85-88 10-7 5-3' n-pentane+3% N.N-di- 36 80 180 370 120-124 90-93 4-3 5-4 methylformamide. I q n-pentane+3% N-rnethyl- 36 80 140 370 117-123 88-92 7-3 5-3 pyrrolidoue! 1 In these cases the catalyst is introduced in vapor form separately into the reaction zone.

' E e tile. .0 The reaction vessel described-in Example l'is heated externally to 480? C. and into the upper opening of the tube there is led per hour-a vaporous mixture of 66.

grams of cyclopentadieneZand 0.2 gram (about "0.3% by weight) of triethylaminei' As the'mixture is introduced into the tube itis preheated incountercurrent to about 460 C. by the-vapors leaving the tube. to. he... flowo h sv l pc e e containing y t through the reaction zone there is"also introduced at the same time 270 liters of chlorine per hour into the reaction vessel} The vapors leaving at'thelower end of the tube are cooled ,to about to C. Asa condensate there are obtained per hour on an average about 248 to 253 remainder consists if-components of higher boiling point which-can readily b;e'separatejd by distillation.

' I Exampiell 4.

In cocurrent (Cyclopentadiene is vaporized v-and, thevapor heated to. 300 C. in'aprelieater. The vapor is then ledinto a' pentadienes of a lower degree of chlorination and 3 to meric hexachlorcyclopentadiene.

5 Example-12 300 liters of chlorine, 40 liters of nitrogen and 66; grams of cyclopentadiene vapor .which with 3% by weight, of N.N-dirnethylformamide have been mixed are led per hour into the'top of a tubeof ceramic material 2000 40 long and 28 mm. in diameter which is arranged vertically andyheated exterrially'tof365 C.- ;After cooling the;ivapors leaving the lower end of the tubeto room temperature, there are obtained per hour 268 grams of a liquid reaction mixture. The mixture consists to the extent of gr The liquid Eamon producticonsists t the extent 8 about 92 to 94% by weight of hexachlorcyclopentadiene on about '90 to 91% of. hexachlorcyclopentadiene; the

"and about 8 to 6% by weight of products of higher boiling point of which the bulkis dimeri"hexachlorcyclopentadiene.

By using the initial hydrocarbons and catalysts enumerated in the following table in the reaction with chlor-inein the manner above described, the results given are obtained at the reaction temperatures specified:

content of liquefied reaction 5 r- ....P 9

3 i s! j i amount 6 reaction liquefied 4 Example hydrobarbon-t percent by added nitrogen chlorine temperreaction hexachlorother compounds weight of catalyst g./1. Llh. 1./h. aturef C, products cyclopentachlorinated of higher 3 1 r g. /h. diene in hydroboiling g percent carbons in point in by weight percent percent w -by weight by weight peultfiaile+2% of dlbutyl- 36 40 160 375 118-121 88-90 6-4 6-5 1 .m pel11511Bn+2% 0f butylpyr- 36 40 160 375 117-120 87-90 .6-3 6-5 ro e. t. pentane|-3% of N.N-di- 36 20 180 375 118-120 [86-89 9-7 5-3 butyltormamide. pntane-l-4'7 N 0 36 20 180 375 119-124 90-94 5-2 I 5-3 cyc1opentadieue+1% 0f tri- 66 l 240 360 268-271 ,92-94 7-6 ethylamine. I 1 M f dicyclo entadiene+2% of 66 80 240 V 400 267-270 -94 9-5 cyclo exylamine. dicyclopentadiene-i-iiZ, of 66 40 280 370 268-271 90-92 I 9-7 N.N-dibuty1formam1de. dicyclopentadiene+3% of 66 40 280 375 265-269 91-94 .8-5' N-methyliormamide.- a v v dicyc1opentadieue+4% N 0, 66 40 240 v 375 268-270 93-96 6-4 2-methylbutane+3%NO 36 40 375 116-119 84-87 11-8 ,5-3 2-methy1butane+2% of cy- 36 40 160 375 117-119 1 .84-86 11-7 1 '5-3 clohexylamine. a p,

7 Example 24 :A verticallyarranged tube of ceramic material 28 mm. in-diameter and 200 mm. in length is heated externally to 380 C. byan electrical resistance heating. Through this q lo oyolopentadiene- I Moreover it contains about 2 to. y weight tl ssh shiy ch or na d QY1QPmedienes and 3 to 4% by weight of ,compoundsofi higher, boiling point. By fractionalrdistillationthe small amount. ofless.

tube'from the top there are led hourly 36 grams of normal 5 g f g fs g g fi e 3?" pentane as vapor and dilutedwith 20 liters of nitrogen an cast rs F t- 1 9 While. at the same time 160 grams of chlorine and 1.8 compqundsq P F P Pmmtemmum the body'of ams of vaporous nitrosyl chloride per hour are supplied g gg 9 a-hath lempictamle 9 separately, tothe reaction tube. The vapors leaving the 011 f lower end of the tube are cooled to 20 C., whereby part 10 The F hlghly chtmmatqd 'cyelopemadlenes after thereof liquefies. On an average there are obtained per eYapommn F be .mlxed wlth dlcyclopema' hour about 125 to 128 grams of liquid reaction product dlene and agam supphedto further T which consists to the extent of 90 to 93% by weight of Further examples are Fonected m the fqllowmg table hexachlorcyclopentadiene, 4 to 5% of chlorinated ali-. 1 These examples are earned. out supplymg to top phatic hydrocarbons, mainly polychlorpentanes, and 5 to 5 of the reacilon' vessel descnbpd Example 31 Pei-{hour 6% of compounds of higher boiling point partly dimeric at F'l f t glven the the hexachlorcyclopentadiene conslsting of initial hydrocarbon and catalyst 1n the The chlorinated aliphatic hydrocarbons can be mixed amounts g1ven table Whll? Smmltaneously chlorine in the reaction of fresh vaporous normal pentane. 90 and P 1 3 mtl'ogell led Into the p of tube The fraction which remains gaseous when the vaporous separately In the mb. m The Workmg P qi mixture i l d may b i part li d to a of the vaporous reaction mixture leaving the tube'at' the fresh reaction. b ttom takes-place n the-way described in (Example '31-. Further examples are given in the following table: The condensed portion of-the-reaction mixtureobtained content of liquefied reaction product in amount reaction liquefied Exhydrocarhon+percent by added nitrogen chlorine temperreaction hexachlorchlorinated compounds. ample weight of catalyst g./h. l./h. 1./h. ature products cycloaliphatic or higher C. in g./h. pentadienehydroboiling in percent carbons point in by weight inpercent; percent by by weight weight nentane+3% N0 36 80 160 400 125-129 91-94 6-3 3-2 n-pentane+5% N0, as 40 180 375 118-122 90-93. 1 6-3 4-2 n-pentane+3% NOr'Cl 36 60 160 380 119-123 89-92 5-3' 5-4 dicyclopentadiene-i-SZ, NO. 66 100 240 350 268-272 95-97' 1 3-5' diIcI 6cgipentad iene+3% 66 50 210 375 267-271 95-96. 7 4-5 diee1ii ntad1e e+N0O1. 66 300 400 266-270 94-96 4+6 Example 31 er hour by cooling and the composition of theliqueficd Through a-vertioally arranged tube of ceramic material mixture are, given inihe table:

content of liquefied reaction product in:

amount reaction liquefied 'Examhydrocarbon+percent by added nitrogen chlorine temperreaction hexachlorless highly substances pie weight of catalyst g./h. L/h. l.lh. ature products cyclopenchlorinated ofhigher C. g./g. tedienein cyclopenboiling percent by tadienes in point in weight percent by percent by weight weight 7 V dicyclopentadiene 66- 32 l mane -1 20 240 400 269-271 95-98 2-4 DIOD 0 n-pentane 36 33 infirm, -1 180 360 120-123 88-90 5-7 4-5 808 0 cyclopentane 35 '94 200 405 128-132 92-93 4-5 nitrogen monoxide 1. 4 cyelopentene 34 .35 180 375 121-124: 90-93 5-6 nitrogen monoxide 1. 4 mixture of 85% n-pentane, 36

12% 2-methylbutane, 3% 3c fig aliphatic hydmm 40 180 380 118-121 89-91 5-7 triethylamine 0. 7

of' a diameter of 28 mm. and a length of 2000mm. which Example 37 is'heated externally to 400 C. there are led from the top The vapors of 66 grams of cyclopemadiene and 2 each hour the vapor of 66 grams of dicyclopentadiene f 2 h 1h 1 which are diluted .with 50 liters of nitrogen and have grams 9 y exy I, lch have been been preheated to 400 C. in a heated vaporizer. At the heated m a preheater heated O are led Per hour same time there are supplied to the tube each hour 240 dowflwardly.through vertlqauyl arranged tube of C6- liters of gaseous chlorine and through a further Supply 70 ramic material 28 mm. in diameter. and 2000 mm. in

2' grams of diethyla-rnine in vapor form. The vapors leaving the lower end of; the tube are cooled to 20 to 25 C., whereby ion an average about 266 to 268 grams of liquid separate per hour. The liquid reaction product length which is heated externally to 375 C. At the same time there are supplied to the tube 275 liters per hour of gaseous chlorine. The .vapo'rs leaving the lower end of the tube are cooledztor25 to 30C., whereby on CDDSJZSISJO..i.h..Kint..0f..92.1Q 94.%.,by weight othexa- .75.. an v ra e 310 lfisr .1 91. hour. of iq id separate. {Ihe' 'liquid reaction product, consists to the extent of'89 to 90% by weight of hexachlorcyclopentadiene.

Moreover there are obtained about3 to 5%. by weight; of cyclo'pentadienes of a lower degree of chlorination and 3 to 5% by weight of constituents of higher boiling point.

We claim: I v I 1. A process for the continuous production of hexachlorcyclopentadiene by the reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cyclopentane, cyclopentene, cyclopentadiene,

and dicyclopentadiene and mixtures of the same, with amines having-5-6 carbons in the cyclic ring with -2' alkyl groups of 1-4 carbons substituted on the carbons of the cyclic ring and 0-2 N-alkyl groups of 1-4 carbons, anilines .with 0-2 N-alkyl groups of 1 -4 carbons, heterocyclic amines having 4- 6, carbons and an amino nitrogen in the heterocyclic ring with 01 alkyl group of l -4 carbons, benzonitrile, 'alkanyl and. alkenyl nitriles with up to 8 carbons, formamides containing 0-2 N-alkyl groups of 1-4 carbons, pyrrolidone, and N-alkylpyrrolidone wherein the alkyl group contains 1-4 carbons so that the reaction components and the catalyst migrate simultaneously through the zone in homogeneous vapor phase, the reaction mixture leaving the zone in vapor phase is cooled and hexachlorcyclopentadiene -is separated from the condensate.

2. A process according to claim 1 wherein the initial hydrocarbon and gaseous chlorine are used in the molar ratio 1:8 to 1:15.

3. A process according to claim 1 wherein the catalyst is used in an amount of 0.2 to about 10% by weight with reference to the amount of hydrocarbon to be reacted.

4. A process according to claiml wherein there is used as the initial hydrocarbon an alkane with carbon atoms of which at least 4 carbon atoms are arranged in a straight chain.

5. A process as claimed in claim 1 wherein cyclopentadiene serves as the initialhydrocarbon.

6. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cyclopentane, cyclopentene, cyclopentadiene, dicyclopentadiene and mixtures of the same with chlorine in the presence of a catalyst at a temperature of about 300 to 500 C., wherein the vapor of the initial hydrocarbon is brought together in a reaction zone heated to the reaction temperature with chlorine and at least one oxide of nitrogen as catalyst, the reaction mixture is Withdrawn from the zone and cooled, and the hexachlorcyclopentadiene is separated from the liquid reaction product.

7. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cyclopentane, cyclopentene, cyclopentadiene, dicyclopentadiene and mixtures of the same, with chlorine in the presence of a catalyst at a temperature of about 300 to 500 C., wherein the vapor of the initial hydrocarbon is brought together in a reaction zone heated to reaction temperature with chlorine and the vapor of a nitrogen oxychloride as catalyst, the reaction mixture is withdrawn from the zone and cooled and the hexachlorcyclopentadiene is separated from the liquid reaction product.

8. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cyclopentane, cyclopentene, cyclopentadiene, dicyclopentadiene and mixtures of the same, with chlorine in the presence of a catalyst at a temperature of about 300 to 500 C., wherein the vapor of the initial hydro'carbon' cooled and the hexachlorcyclopentadiene is separated from the liquid reaction product.

9. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cyclopentane, cyclopentene, cyclopentadiene, dicyclopentadiene and mixtures of the same, with chlorine in the presence of a catalyst at a temperature of about 300 to 500 C., wherein the vapor of the initial hydrocarbon is brought together in a reaction zone heated to the reaction temperature with chlorine and benzonitrile vapor as a catalyst, the reaction mixture is withdrawn from the zone and cooled and hexachlorcyclopentadiene is separated from the liquid reaction product.

10. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cy-

clopentane, cyclopentene, cyclopentadiene, dicyclopenta-' diene and mixtures of the same, with chlorine in the presence of a catalyst at .a temperature of about 300 to 500 C., wherein the vapor of the initial hydrocarbon is brought together in a reaction zone heated to the reaction temperature with chlorine and the vapor of at least one alkyl nitrile with 1 to 8 carbon. atoms in the alkyl radical, the reaction mixture is withdrawn from the zone and cooled and the hexachlorcyclopentadiene is separated from the liquid reaction product.

11. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cyclopentane, cyclopentene, cyclopentadiene, dicyclopentadiene and mixtures of the same, with chlorine in the presence of a catalyst at a temperature of about 300 to 500 C., wherein the vapor of the initial hydrocarbon is brought together with chlorine and the vapor of a fo'rmamide having 0-2 N-alkyl groups of 1-4 carbons as a catalyst in a reaction zone heated to reaction temperature, the reaction mixture is withdrawn from the reaction perature with chlorine and the vapor of pyrolidone as a catalyst, the reaction mixture is withdrawn from the zone and cooled and the hexachlorcyclopentadiene is separated from the liquid reaction product.

13. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbonfrom the group consisting of normal pentane, isopentane, cyclopentane, cyclopentene, cyclopentadiene, dicyclo'pentadiene and mixtures of the same, with chlorine in the presence of a catalyst at a temperature of about 300 to 500 C., wherein the vapor of the initial hydrocarbon is brought together in a reaction zone heated to the reactio'n temperature with chlorine and the vapor of a cycloalkyl amine having 5-6 carbons in the cyclic ring with 0-2 alkyl groups of 1-4 carbons on the carbons of the cyclic ring and 0-2 N-alkyl groups of 1-4 carbons as catalyst, the reaction mixture is withdrawn from the zone and cooled and the hexachlorcyclopentadiene is separated from the liquid reaction product.

14. A process for the production of hexachlorcyclo- 11 pentadiene. by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane,isopentane,.cyclopentane, cyclo'pentene, cyclopentadiene, dicyclopentadiene and mixtures of the same, with- Chlorine in the 15. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cyclo'pentane, cyclopentene, cyclopentadiene, dicyclopentadiene and mixtures of the same, with chlorine in the presence of a catalyst at a temperature of about 300 to 500 (3., wherein the vapor of the initial hydrocarbon is brought together in a reaction zone heated to the reaction temperature with chlorine and the vapor of acrylonitrile, the reaction mixture is Withdrawn from the zone and cooled and the hexachlorcyclopentadiene is separated from the liquid reaction product.

16. A process for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cy-

clopentane, .cyclopentene, cyclopentadiene, dicyclopentadiene and mixtures of .thesame; with chlorine in the presence .of acatalyst at antemperature of about 300 to 500' (3., whereinthe vapor of the initial hydrocarbon is brought together in a reaction zone heated to the reaction temperature with chlorine and the vapor of methacrylonitrile, the reaction mixture is withdrawn from the zone and cooled, and the hexachlorcyclopentadiene is separated from the liquid reaction product.

I 17. .A pro'cess for the production of hexachlorcyclopentadiene by reaction of an aliphatic hydrocarbon from the group consisting of normal pentane, isopentane, cyclopentane, cyclopentadiene, dicyclopentadiene and mixtures of the same, with chlorine in the presence of a catalyst at a temperature of about 300 to 500 C.,

References Cited in the file of this patent UNITED STATES PATENTS Kleiman Nov. 3, 1953 Wetrotf et a1 June 11, 1957 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Now,v 2 945 893 Adolf Steinhofer et al8 July 19 1960 It is hereby certified that error appears in the-printed specification" 8 of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns 7 and 8, second table seventh column thereof in the heading, for "liquefied reaction products g./g." read liquefied reaction products g./h.

Signed and sealed this 10th day of January 1961.,

(SEAL) Attest:

KARL H, AXLINE v ROBERT C. WATSON Commissioner of Patents Attesting ()flicer 

1. A PROCESS FOR THE CONTINUOUS PRODUCTION OF HEXACHLORCYCLOPENTADIENE BY THE REACTION OF AN ALIPHATIC HYDROCARBON FROM THE GROUP CONSISTING OF NORMAL PENTANE, ISOPENTANE, CYCLOPENTANE, CYCLOPENTENE, CYCLOPENTADIENE, AND DICYCLOPENTADIENE AND MIXTURES OF THE SAME, WITH CHLORINE IN THE PRESENCE OF A CATALYST AT A TEMPERATURE OF ABOUT 300*C. TO 500*C., WHEREIN THE VAPOR OF THE INITIAL HYDROCARBON IS CONTINUOUSLY BROUGHT TOGETHER IN A REACTION ZONE HEATED TO THE REACTION TEMPERATURE WITH CHLORINE AND, AS CATALYST, WITH THE VAPOR OF AT LEAST ONE NITROGENOUS COMPOUND FROM THE GROUP CONSISTING OF OXIDES OF NITROGEN, NITROGEN OXYCHLORIDES, ALKYL AMINES WHEREIN THE ALKYL GROUPS HAVING 1-8 CARBONS, CYCLOALKYL AMINES HAVING 5-6 CARBONS IN THE CYCLIC RING WITH 0-2 ALKYL GROUPS OF 1-4 CARBONS SUBSTITUTED ON THE CARBONS OF THE CYCLIC RING AND 0-2 N-ALKYL GROUPS OF 1-4 CARBONS, ANILINES WITH 0-2 N-ALKYL GROUPS OF 1-4 CARBONS, HETEROCYCLIC AMINES HAVING 4-6 CARBONS AND AN AMINO NITROGEN IN THE HETEROCYCLIC RING WITH 0-1 ALKYL GROUP OF 1-4 CARBONS, BENZONITRILE, ALKANYL AND ALKENYL NITRILES WITH UP TO 8 CARBONS, FORMAMIDES CONTAINING 0-2 N-ALKYL GROUPS OF 1-4 CARBONS, PYRROLIDONE, AND N-ALKYLPYRROLIDONE WHEREIN THE ALKYL GROUP CONTAINS 1-4 CARBONS SO THAT THE REACTION COMPONENTS AND THE CATALYST MIGRATE SIMULTANEOUSLY THROUGH THE ZONE IN HOMOGENEOUS VAPOR PHASE, THE REACTION MIXTURE LEAVING THE ZONE IN VAPOR PHASE IS COOLED AND HEXACHLORCYCLOPENTADIENE IS SEPARATED FROM THE CONDENSATE. 